Unexpected kinetically controlled organoselenium-based isomaleimide: X-ray structure, hirshfeld surface analysis, 3D energy framework approach, and density functional theory calculation.

Reduction of 4,4'-diselanediyldianiline (1) followed by the reaction with bromo-4-(bromomethyl)benzene afforded the corresponding 4-((4-bromobenzyl)selanyl)aniline (2) in 85% yield. N-Maleanilic acid 3 was obtained in 94% yield via the reaction of selenoamine 2 with toxilic anhydride. Subsequent dehydration of N-maleanilic acid 3 using acetic anhydride furnished the unexpected isomaleimide 5-((4-((4-bromophenyl)selanyl)phenyl)imino)furan-2(5H)-one (4) instead of the maleimide 5. The molecular structure of compound 4 was confirmed by mass spectrometry, 1H- and 13C-NMR spectroscopy, and X-ray diffraction analysis. Their cytotoxicity was assessed against two oligodendrocytes, and their respective redox properties were evaluated using 2',7'-dichlorodihydrofluorescein diacetate (H2-DCFDA) assay. Furthermore, their antiapoptotic potential was also evaluated by flow cytometry. The compound crystallizes in triclinic P-1 space group with unit cell parameters a = 5.7880 (4) Å, b = 9.8913 (6) Å, c = 14.5951 (9) Å, V = 1731.0 (3) Å3 and Z = 2. The crystal packing is stabilized by intermolecular hydrogen bonding, π···π, C-Br···π stacking interactions, and other non-covalent interactions. The mapping of different Hirshfeld surfaces and 2D-fingerprint were used to investigate intermolecular interactions. The interaction energies that stabilize the crystal packing were calculated and graphically represented as framework energy diagrams. We present a computational investigation of compound 4's molecular structure at the Density Functional Theory level using the B3LYP method and the 6-31G ++ basis set in this paper. The optimized structure matches the experimental outcome. The global reactivity descriptors and molecular electrostatic potential (M.E.P.) map emphasize the molecule's reactive locations, allowing reactivity prediction. The charge transfer properties of molecules can be estimated by examining Frontier molecular orbitals.

New Organic-Inorganic Salt Based on Fluconazole Drug: TD-DFT Benchmark and Computational Insights into Halogen Substitution.

In this study, we report the synthesis of a new organic-inorganic molecular salt of the clinically used antifungal drug fluconazole, (H2Fluconazole).SnCl6.2H2O. By detailed investigation and analysis of its structural properties, we show that the structure represents a 0D structure built of alternating organic and inorganic zig-zag layers along the crystallographic c-axis and the primary supramolecular synthons in this salt are hydrogen bonding, F···π and halogen bonding interactions. Magnetic measurements reveal the co-existence of weak ferromagnetic behavior at low magnetic field and large diamagnetic contributions, indicating that the synthesized material behaves mainly as a diamagnetic material, with very low magnetic susceptibility and with a band gap energy of 3.6 eV, and the salt is suitable for semiconducting applications. Extensive theoretical study is performed to explain the acceptor donor reactivity of this compound and to predict the Cl-substitution effect by F, Br and I. The energy gap, frontier molecular orbitals (FMOs) and the different chemical reactivity descriptors were evaluated at a high theoretical level. Calculations show that Cl substitution by Br and I generates compounds with more important antioxidant ability and the intramolecular charge transfer linked to the inorganic anion.

A Competition between Hydrogen, Stacking, and Halogen Bonding in N-(4-((3-Methyl-1,4-dioxo-1,4-dihydronaphthalen-2-yl)selanyl)phenyl)acetamide: Structure, Hirshfeld Surface Analysis, 3D Energy Framework Approach, and DFT Calculation.

N-(4-((3-Methyl-1,4-dioxo-1,4-dihydronaphthalen-2-yl)selanyl)phenyl)acetamide (5), C19H15NO3Se, was prepared in two steps from 4,4'-diselanediyldianiline (3) via reduction and subsequent nucleophilic reaction with 2-methyl-3-bromo-1,4-naphthalenedione, followed by acetylation with acetic anhydride. The cytotoxicity was estimated against 158N and 158JP oligodendrocytes and the redox profile was also evaluated using different in vitro assays. The technique of single-crystal X-ray diffraction is used to confirm the structure of compound 5. The enantiopure 5 crystallizes in space group P21 with Flack parameter 0.017 (8), exhibiting a chiral layered absolute structure. Molecular structural studies showed that the crystal structure is foremost stabilized by N-H···O and relatively weak C-H···O contacts between molecules, and additionally stabilized by weak C-H···π and Se···N interactions. Hirshfeld surface analysis is used to quantitatively investigate the noncovalent interactions that stabilize crystal packing. Framework energy diagrams were used to graphically represent the stabilizing interaction energies for crystal packing. The analysis of the energy framework shows that the interactions energies of and C-H···π and C-O···π are primarily dispersive and are the crystal's main important forces. Density functional theory (DFT) calculations were used to determine the compound's stability, chemical reactivity, and other parameters by determining the HOMO-LUMO energy differences. The determination of its optimized surface of the molecular electrostatic potential (MEP) was also carried out. This study was conducted to demonstrate both the electron-rich and electron-poor sites.

One-Dimensional Organic-Inorganic Material (C6H9N2)2BiCl5: From Synthesis to Structural, Spectroscopic, and Electronic Characterizations.

The new organic-inorganic compound (C6H9N2)2BiCl5 (I) has been grown by the solvent evaporation method. The one-dimensional (1D) structure of the allylimidazolium chlorobismuthate (I) has been determined by single crystal X-ray diffraction. It crystallizes in the centrosymmetric space group C2/c and consists of 1-allylimidazolium cations and (1D) chains of the anion BiCl52-, built up of corner-sharing [BiCl63-] octahedra which are interconnected by means of hydrogen bonding contacts N/C-H⋯Cl. The intermolecular interactions were quantified using Hirshfeld surface analysis and the enrichment ratio established that the most important role in the stability of the crystal structure was provided by hydrogen bonding and H···H interactions. The highest value of E was calculated for the contact N⋯C (6.87) followed by C⋯C (2.85) and Bi⋯Cl (2.43). These contacts were favored and made the main contribution to the crystal packing. The vibrational modes were identified and assigned by infrared and Raman spectroscopy. The optical band gap (Eg = 3.26 eV) was calculated from the diffuse reflectance spectrum and showed that we can consider the material as a semiconductor. The density functional theory (DFT) has been used to determine the calculated gap, which was about 3.73 eV, and to explain the electronic structure of the title compound, its optical properties, and the stability of the organic part by the calculation of HOMO and LUMO energy and the Fukui indices.

Synthesis, crystal structure and Hirshfeld surface analysis of bis-{2-[(pyridin-2-yl)amino]-pyridinium} tetra-cyano-nickelate(II).

In the title mol-ecular salt, (C10H10N3)2[Ni(CN)4], the dihedral angle between the pyridine rings in the cation is 1.92 (13)° and the complete anion is generated by a crystallographic centre of symmetry. An intra-molecular N-H⋯N hydrogen bond occurs in the cation, which closes an S(6) ring. In the crystal, the components are linked by N-H⋯N and weak C-H⋯N hydrogen bonds, which generate chains propagating in the [101] direction. Weak aromatic π-π stacking inter-actions are also observed. A Hirshfeld surface analysis and two-dimensional fingerprint plots indicate that the most important contact types in the crystal packing are N⋯H/H⋯N, C⋯H/H⋯C and H⋯H with contributions of 37.2, 28.3 and 21.9%, respectively.

Crystal structure, optical property and Hirshfeld surface analysis of bis-[1-(prop-2-en-1-yl)-1H-imidazol-3-ium] hexa-chlorido-stannate(IV).

A new 0D organic-inorganic hybrid material bis-[1-(prop-2-en-1-yl)-1H-imidazol-3-ium] hexa-chlorido-stannate(IV), (C6H9N2)2[SnCl6], has been prepared and characterized by single-crystal X-ray diffraction, Hirshfeld surface analysis and UV-visible spectroscopy. The structure consists of isolated [SnCl6]2- octa-hedral anions separated by layers of organic 1-(prop-2-en-1-yl)-1H-imidazol-3-ium cations. The 1-(prop-2-en-1-yl) fragment in the organic cation exhibits disorder over two sets of atomic sites having occupancies of 0.512 (9) and 0.488 (9). The crystal packing of the title compound is established by inter-molecular N/C-H⋯Cl hydrogen bond and π- π stacking inter-actions. Hirshfeld surface analysis employing three-dimensional mol-ecular surface contours and two-dimensional fingerprint plots has been used to analyse the inter-molecular inter-actions present in the structure. The optical properties of the crystal were studied using UV-visible absorption spectroscopy, showing one intense band at 208 nm, which is attributed to π-π* transitions in the cations.

Broad-band luminescence involving fluconazole antifungal drug in a lead-free bismuth iodide perovskite: Combined experimental and computational insights.

The synthesis and characterization of a lead-free perovskite-type material, (C13H14N6F2O)2 Bi2I10 is reported. It exhibits a zero-dimensional (0D) Bi2I104- octahedral unit, surrounded by a flexible tripodal antifungal ligand (H2Fluconazole)2+. The several intermolecular interactions of the independent cation and the bismuth iodide octahedra were tested via the Hirshfeld surface analysis. The detailed interpretation of the vibrational modes was carried out. The band gap (Eg) of 2.10 eV agrees with the theoretical values. Upon photoexcitation, the crystals exhibit a broadband green emission peaked at 534 nm, which originates from electronic transitions within the inorganic cluster [Bi2I10]4-. The theoretical calculations were carried out using DFT and TD-DFT methods to appraise the molecular geometry, vibrational spectra, electronic absorption spectra, frontier molecular orbitals (FOMs) and global reactivity descriptors. Calculations reveal that the energy gap (Eg) and other chemical reactivity descriptors are primarily linked to the inorganic anion and the triazolium rings (A and B) of the organic cation reflecting their importance in the activity and the antioxidant ability of the molecule.

Crystal structure, Hirshfeld surface analysis and physicochemical characterization of bis-[4-(di-methyl-amino)-pyridinium] di-µ-chlorido-bis[di-chlorido-mercurate(II)].

The title mol-ecular salt, (C7H11N2)2[Hg2Cl6], crystallizes with two 4-(di-methyl-amino)-pyridinium cations (A and B) and two half hexa-chlorido-dimercurate(II) anions in the asymmetric unit. The organic cations exhibit essentially the same features with an almost planar pyridyl ring (r.m.s. deviations of 0.0028 and 0.0109 Å), which forms an inclined dihedral angle with the dimethyamino group [3.06 (1) and 1.61 (1)°, respectively]. The di-methyl-amino groups in the two cations are planar, and the C-N bond lengths are shorter than that in 4-(di-methyl-amino)-pyridine. In the crystal, mixed cation-anion layers lying parallel to the (010) plane are formed through N-H⋯Cl hydrogen bonds and adjacent layers are linked by C-H⋯Cl hydrogen bonds, forming a three-dimensional network. The analyses of the calculated Hirshfeld surfaces confirm the relevance of the above inter-molecular inter-actions, but also serve to further differentiate the weaker inter-molecular inter-actions formed by the organic cations and inorganic anions, such as π-π and Cl⋯Cl inter-actions. The powder XRD data confirms the phase purity of the crystalline sample. Furthermore, the vibrational absorption bands were identified by IR spectroscopy and the optical properties were studied by using optical UV-visible absorption spectroscopy.